US20240076257A1 - Process for preparing bisphenol a (bpa) in the presence of 2-methyl benzofuran - Google Patents
Process for preparing bisphenol a (bpa) in the presence of 2-methyl benzofuran Download PDFInfo
- Publication number
- US20240076257A1 US20240076257A1 US18/270,646 US202218270646A US2024076257A1 US 20240076257 A1 US20240076257 A1 US 20240076257A1 US 202218270646 A US202218270646 A US 202218270646A US 2024076257 A1 US2024076257 A1 US 2024076257A1
- Authority
- US
- United States
- Prior art keywords
- para
- ortho
- phenol
- bisphenol
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- GBGPVUAOTCNZPT-UHFFFAOYSA-N 2-Methylcumarone Chemical compound C1=CC=C2OC(C)=CC2=C1 GBGPVUAOTCNZPT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 29
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 239000004417 polycarbonate Substances 0.000 claims abstract description 19
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 93
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 82
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 74
- 239000012535 impurity Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkyl sulfides Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- PBEHQFUSQJKBAS-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 PBEHQFUSQJKBAS-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical group CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229940116441 divinylbenzene Drugs 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- TWNMOFPCODKHLV-UHFFFAOYSA-N 1-benzofuran methanol Chemical compound CO.O1C=CC2=C1C=CC=C2 TWNMOFPCODKHLV-UHFFFAOYSA-N 0.000 description 1
- JGDWYKQLFQQIDH-UHFFFAOYSA-N 2-phenyl-3,4-dihydrochromen-2-ol Chemical class C1CC2=CC=CC=C2OC1(O)C1=CC=CC=C1 JGDWYKQLFQQIDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010543 cumene process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
Definitions
- the present invention relates to a process for preparing bisphenol A and a process for preparing polycarbonate.
- Bisphenol A or BPA is an important monomer in the production of polycarbonate or epoxy resins.
- BPA is used in the form of para,para-BPA (2,2-Bis(4-hydroxyphenol)propane; p,p-BPA).
- ortho-BPA ortho-BPA
- o,o-BPA ortho-BPA
- o,p-BPA ortho-BPA
- BPA is produced by reacting phenol with acetone in the presence of an acid catalyst to give the bisphenol.
- hydrochloric acid (HCl) was used for the commercial process of the condensation reaction.
- HCl hydrochloric acid
- the most important resins are crosslinked polystyrenes with sulfonic acid groups.
- Divinylbenzene is mostly used as the crosslinking agent as described in GB849965, U.S. Pat. No. 4,427,793, EP0007791 and EP0621252 or Chemistry and properties of crosslinked polymers, edited by Santokh S. Labana, Academic Press, New York 1977.
- the reaction of phenol with acetone can be performed in the presence of suitable co-catalyst.
- US2005/0177006 A1 and U.S. Pat. No. 4,859,803 describe a process for preparing bisphenol A in the presence of an ion-exchange catalyst and mercaptopropionic acid or a mercaptan as co-catalyst. It is known that the catalyst deactivates over time. For example, the deactivation is described in EP0583712, EP10620041, DE14312038.
- One major objective for the production process is to maximize the performance and dwell times of the catalyst system. Accordingly, there is a need to identify potential poisonous substances, byproducts, impurities of educts etc. in order to deal with this objective.
- WO2012/150560 A1 teaches the use of a specific catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein the co-catalyst is chemically bound to the ion exchange resin catalyst, and also a process for catalyzing condensation reactions between phenols and ketones using such specific catalyst system. Furthermore WO2012/150560 A1 discloses a process for catalyzing condensation reactions between phenols and ketones that does not utilize a bulk promoter that is not chemically bound to the ion exchange resin catalyst.
- EP1520617 A1 describes a process for preparing bisphenols in the presence of an acidic ion-exchange resin catalyst which is modified with specific cationic compound.
- U.S. Pat. No. 8,247,619B2 describes the production of BPA based on bio-derived phenol and/or bio-derived acetone in the presence bio-derived impurities in the educts.
- This document solely describes the use of an ion exchange resin catalyst with attached promotor meaning that the co-catalyst is chemically (i. e. ionically) bound to the ion exchange resin catalyst.
- 2-Methylbenzofuran (2-MBF or MBF) was found to be a common impurity in fossil fuel-derived but also bio-derived phenol. It was found to react completely during the reaction of phenol and acetone so that no free 2-MBF was detected in the reaction product (BPA). Additionally three new MBF reaction products were observed.
- At least one of the above-mentioned objects, preferably all of these objects have been solved by the present invention.
- a catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound (i. e. not chemically bound) to the ion exchange resin catalyst, is not susceptible to catalyst poisoning by 2-methyl benzofuran.
- the prior art teaches the necessity to reduce the amount of 2-methyl benzofuran in raw phenol as low as possible.
- the prior art teaches that using a catalyst system which comprises an ionic bond between the ion exchange resin and the co-catalyst the MBF fully reacts during the reaction of acetone and phenol.
- the resulting side products of MBF have a negative impact on the color of the BPA and also the resulting BPA PC. It has been surprisingly found that when using a catalyst system, wherein the catalyst system comprises an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part, preferably at least 75 mol-% of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst, the formation of such side products of MBF can be reduced.
- the present invention provides a process for preparing ortho,para-, ortho, ortho- and/or para,para-bisphenol A comprising the step of
- raw phenol and/or “raw acetone”.
- the term “raw” is used for the unreacted educts as applied, especially added, in the process for preparing BPA.
- this term is used to distinguish the phenol which is freshly added to the reaction (as raw phenol) and the phenol which is recycled in the process for preparing BPA (recycled phenol).
- Such recycled phenol cannot add additional MBF to the process.
- acetone which is freshly added to the reaction (as raw acetone) and acetone which is recycled in the process for preparing BPA (recycled acetone).
- phenol and/or acetone without any further specification it is preferred that the sum either the chemical compound as such or both raw and recycled phenol and/or raw and recycled acetone are meant.
- MBF is an impurity in raw phenol which is one of the educts of the reaction of BPA.
- Raw phenol can contain MBF impurities.
- the production pathways for phenol are described in Arpe, Hans-Jürgen, Industrielle Organische Chemie, 6. Auflage, founded 2007, Wiley-VCH.
- the process for preparing phenol is described in Ullmann's Encyclopedia of Industrial Chemistry, chapters Phenol and Phenol derivatives.
- the oxidation of cumene, also known as Hock process is by far the dominant synthetic route to phenol.
- 2-methyl benzofuran is 2-methyl benzofuran.
- the process of the present invention is characterized in that the amount of 2-methyl benzofurane present in step (a) is higher than 1 ppm, preferably higher than 2 ppm, more preferably higher than 3 ppm, still more preferably higher than 4 ppm, still preferably higher than 5 ppm, still more preferably higher than 6 ppm, still more preferably higher than 7 ppm, still more preferably higher than 8 ppm, still more preferably higher than 9 ppm, still more preferably higher than 10 ppm, still more preferably higher than 11 ppm, still more preferably higher than 12 ppm, still more preferably higher than 13 ppm, still more preferably higher than 14 ppm, still more preferably higher than 15 ppm, still more preferably higher than 20 ppm, still more preferably higher than 25 ppm and most preferably higher than 50 ppm with respect to the total weight the raw phenol.
- the amount of MBF present in step (a) is higher than 1 ppm and equal to or lower than 5000 ppm, more preferably equal to or lower 4500 ppm, still more preferably equal to or lower 4000 ppm, still more preferably equal to or lower 3500 ppm, still more preferably equal to or lower 3000 ppm, still more preferably equal to or lower 2500 ppm and most preferably equal to or lower 2000 ppm with respect to the total weight of the raw phenol.
- the upper limits given here can be combined with the preferred lower limits given above can be combined.
- the skilled person knows how to determine the amount of MBF in raw phenol. For example, the amount of 2-methyl benzofuran in raw phenol can be determined according to ASTM D6142-12 (2013).
- ppm preferably refers to parts by weight.
- step (a) is conducted in the additional presence of at least one impurity formed due to the presence of MBF in process step (a). Moreover, those impurities can be present in process step (a) in case the phenol fraction of step (b) is recycled in process step (c).
- the process of the present invention is characterized in that the 2-methyl benzofuran is present throughout the whole process step (a).
- the MBF does not fully react during process step (a). This means that some of the MBF is still present in the BPA.
- Preferably at least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% with respect to the MBF being present at the beginning of process step (a) are present also at the end of process step (a), preferably at the beginning of process step (b) described below.
- At least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% with respect to the MBF being present at the beginning of process step (a) are present in the resulting ortho,para-, ortho, ortho- or para,para-bisphenol A.
- the process of the present invention is characterized in that the process additionally comprises the following step:
- the bisphenol A fraction is taken as product and/or further purified.
- WO-A 0172677 describes crystals of an adduct of a bisphenol and of a phenol and a method for producing these crystals and finally preparing bisphenols. It was found that by crystallizing these adducts a para,para-BPA of high purity can be obtained.
- EP1944284 describes the process for producing bisphenols wherein the crystallization comprises continuous suspension crystallization devices.
- WO-A 2005075397 describes a process for producing bisphenol A in which the water that is produced during the reaction is removed by distillation. By this method the unreacted acetone is recovered and recycled resulting in an economically favorable process.
- the process of the present invention is characterized in that the separation in step (b) is performed using a crystallization technique. Still preferably, the separation in step (b) is performed using at least one continuous suspension crystallization device.
- BPA is taken out of the solvent by crystallization and filtration after the reaction.
- the mother liquor typically contains 5 to 20% BPA and byproducts dissolved in unreacted phenol.
- water is formed during the reaction and is removed from the mother liquor in the dewatering section.
- the fraction comprising unreacted phenol is recycled for further reaction. This preferably means that the mother liquor is recycled. It is re-used as unreacted phenol in the reaction with acetone in order to give BPA.
- the flow of mother liquor is preferably conventionally recirculated into the reaction unit.
- byproducts in the mother liquor are for example o,p-BPA, o,o-BPA, substituted indenes, hydroxyphenyl indanoles, hydroxyphenyl chromanes, substituted xanthenes and higher condensed compounds.
- further secondary compounds such as anisole, mesityl oxide, mesitylene and diacetone alcohol may be formed as a result of self-condensation of the acetone and reaction with impurities in the raw material.
- the process according to the present invention is characterized in that the process comprises the additional step of
- the part of the phenol fraction comprises at least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% of MBF, wherein the weight percent of MBF refers to the part of MBF as compared to the MBF being present in the raw phenol.
- step (a) In order to avoid accumulation of the introduced MBF, byproducts and/or impurities formed due to the presence of MBF in step (a) in the system several options exist. Those options include inter alia the purge stream, the waste water, the off gas and the BPA as product itself. The major one seems to be the purge stream, for example a portion of the mother liquor is discharged.
- Another approach comprises the passing a part of the entire amount of the circulation stream after solid/liquid separation and before or after the removal of water and residual acetone, over e. g. a rearrangement unit filled with acid ion exchanger. In this rearrangement unit some of the byproducts from BPA preparation are isomerized to give p,p-BPA.
- the new impurity which forms due to the presence of MBF in process step (a) can be at least partly removed by a purge stream. Accordingly, it is preferred that at least part of the phenol fraction obtained in step (b) is used as educt in step (a), wherein at least a part of this stream is purged. Preferably, more than 50 vol.-% of the phenol fraction obtained in step (b) is used as educt in step (a), wherein the vol.-% is based on the total volume of the phenol fraction.
- the catalyst system which can be used in the process of the present invention is known by the skilled person.
- it is an acidic ion exchange resin.
- Such ion exchange resin can have from 2% to 20%, preferably 3 to 10% and most preferably 3.5 to 5.5% crosslinkage.
- the acidic ion exchange resin preferably can be selected from the group consisting of sulfonated styrene divinyl benzene resins, sulfonated styrene resins, phenol formaldehyde sulfonic acid resins and benzene formaldehyde sulfonic acid.
- the ion exchange resin may contain sulfonic acid groups.
- the catalyst bed can be either a fixed bed or a fluidized bed.
- the catalyst system of the present invention comprises a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst.
- the sulfur containing cocatalyst can be one substance or a mixture of at least two substances.
- This cocatalyst is preferably dissolved in the reaction solution of process step (a). Still preferably, the cocatalyst is dissolved homogenously in the reaction solution of process step (a).
- the process of the present invention is characterized in that the sulfur containing cocatalyst is selected from the group consisting of mercaptopropionic acid, hydrogen sulfide, alkyl sulfides such as ethyl sulfide and mixtures thereof. Most preferably, the sulfur containing cocatalyst is 3-mercaptopropionic acid.
- the catalyst system of the present invention comprises a sulfur containing cocatalyst, wherein all of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst.
- the expression “not chemically bound” or “neither covalently nor ionically bound” refers to a catalyst system where neither a covalent nor an ionic bound between the ion exchange resin catalyst and the sulfur containing cocatalyst is present at the beginning of process step (a).
- the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst.
- the mol-% relate to the total sum of the cocatalyst present in process step (a).
- MBF is a common impurity in raw phenol
- the MBF present in step (a) is introduced into the process step (a) as impurity in the raw phenol.
- at least part of the MBF can be present in process step (a) due to other reasons.
- some of the MBF present in process step (a) may be present due to the recycling of phenol.
- the process according to the present invention is characterized in that the raw phenol which is used in process step (a) is bio-based. Still preferably, the raw phenol which comprises MBF as impurity is bio-based.
- bio-derived or “bio-based” refers to (raw) phenol from a currently renewable resource. In particular, this term is used as opposed to phenol being derived from fossil fuels.
- the fact whether a raw material is bio-based can be verified by measurements on carbon isotope levels, since the relative amounts of isotopic carbon C 14 are lower in fossil-fuel materials. The skilled person knows such measurements which can be performed for example according to ASTM D6866-18 (2016) or 15016620-1 to -5 (2015).
- the present invention provides a process for preparing polycarbonate comprising the steps of
- the process for the production of ortho,para-, ortho, ortho- and/or para,para-bisphenol A of the present invention provides a BPA which can be obtained in a more economical and/or ecological way. Accordingly, in using this BPA as obtained with the process according to the present invention, the process for preparing polycarbonate according to the present invention is more economical and/or ecological, too.
- Reaction step (ii) is known to the skilled person.
- the polycarbonates can be prepared in a known manner from the BPA, carbonic acid derivatives, optionally chain terminators and optionally branching agents by interphase phosgenation or melt transesterification.
- interphase phosgenation bisphenols and optionally branching agents are dissolved in aqueous alkaline solution and reacted with a carbonate source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture comprising an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound.
- a carbonate source such as phosgene
- the reaction procedure can also be effected in a plurality of stages.
- Such processes for the preparation of polycarbonate are known in principle as interfacial processes, for example from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 page 33 et seq., and on Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, chapter VIII, page 325, and the underlying conditions are therefore familiar to the person skilled in the art.
- polycarbonates may also be prepared by the melt transesterification process.
- the melt transesterification process is described, for example, in Encyclopaedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol, 9, John Wiley and Sons, Inc. (1964), and DE-C 10 31 512.
- the aromatic dihydroxy compounds already described in the case of an interfacial process are transesterified with carbonic acid diesters with the aid of suitable catalysts and optionally further additives in the melt.
- the process for preparing polycarbonates according to the present invention is characterized in that the process step (i) further comprises a step of purifying the ortho,para-, ortho, ortho- and/or para,para-bisphenol A in order to reduce the amount of at least one impurity formed due to the presence of MBF in step (a).
- the process step (i) further comprises a step of purifying the ortho,para-, ortho, ortho- and/or para,para-bisphenol A in order to reduce the amount of at least one impurity formed due to the presence of MBF in step (a).
- cheaper raw phenol can be used in the process of the present invention.
- other impurities are formed. These impurities are preferably removed before the polymerization.
- catalyst acidic polymer-based resin polystyrene-divinyl-benzene
- sulfonic acid groups spherical beads
- spherical beads 4% of crosslinking, phenol Acros Organics, grade: extra pure > 99% (measured purity by GC: 99.9%) MEPA 3-mercaptopropionic acid, Sigma-Aldrich, Purity > 99% (measured purity by GC: 99.3%) acetone VWR, GPR rectapur > 99.5% (measured purity by GC: 100%, water not included) 2-methyl Sigma Aldrich, purity 99.0% benzofuran methanol Fisher Analytical grade; GC purity 99.99%
- a column reactor was equipped with 150 g of the phenol-wet catalyst (volume of phenol-wet catalyst in the reactor: 210 to 230 ml). The column reactor was heated to 60° C. (catalyst bed temperature during reaction: 63° C.). A mixture of phenol, acetone (3.9 wt.-%) and MEPA (160 ppm with respect to the sum of the masses of phenol and acetone) was prepared and tempered to 60° C. This mixture was pumped into the column reactor with a flow rate of 45 g/h. The column reactor was equipped with a sampling point at the bottom. Using the aperture of the sampling point, different samples were taken during the reaction. Sampling time was 1 h and the amount of the sample taken each hour was 45 g.
- a first run (standard run) was conducted for 52 h. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken and analyzed via GC.
- a second run (impurity run) was conducted for 52 h.
- 1590 ppm (with respect to the sum of the masses of phenol and acetone) of 2-methyl benzofuran was dosed to the reaction system.
- a sample was taken and analyzed via GC.
- phenol and MEPA was used and a third run (standard run) was conducted for 52 h.
- a sample was taken via a syringe and analyzed via GC. Then a fourth run (impurity run) was conducted for 52 h.
- the gaschromatography (GC) for methanol was conducted using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 50 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m, a temperature profile of 60° C. for 0.10 min, heating with 12° C./min to 320° C. and holding this temperature for 10.00 min; injecting 1 ⁇ l with a split of 10/1 at 300° C.); wherein the flow is 2 ml/min at an initial pressure of 18.3 psi (1.26 bar)
- the gaschromatography (GC) for 2-methyl benzofuran, phenol, para,para BPA were conducted using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 50 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m, a temperature profile of 80° C. for 0.10 min, heating with 12° C./min to 320° C. and holding this temperature for 10.00 min; injecting 1 ⁇ l with a split of 10/1 at 300° C.); wherein the flow is 2 ml/min at an initial pressure of 18.3 psi (1.26 bar)
- the gas chromatography (GC) coupled to mass spectroscopy (MS) for identification of the unknown compound was performed using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 30 m ⁇ 0.25 mm ⁇ 0.25 ⁇ m, a temperature profile of 60° C. for 0.10 min, heating with 12° C./min to 350° C. and holding this temperature for 5 min; injecting 0.5 ⁇ l with a split of 10/1 at 250° C.); wherein the flow is 1 ml/min at an initial pressure of 24.45 psi (1.685768 bar) and the mass spectrometer scans from mz35-mz 700.
- Agilent J&W VF-1MS 50% Dimethylpolysiloxane
- the standard run represents the reaction of acetone and phenol in the presence of the catalyst and cocatalyst to form BPA. From this the acetone conversion can be estimated including respective error bars. This conversion represented the baseline to evaluate whether the impurities influence the catalyst deactivation or not.
- the acetone conversion of standard runs 3 and 5 were compared to the value of standard run 1 to determine the effect of 2-methyl benzofuran on the catalyst. If the acetone conversion dropped out of this conversion, it would be proven that 2-methyl benzofuran has an effect on the BPA catalyst. In order to show that this kind of evaluation can be used to determine catalyst poisoning, a reference run was conducted using methanol as impurity.
- the following table shows the results of the first run (standard run), the second run (impurity run), the third run (standard run), the fourth run (impurity run) and the fifth run (standard run) for 2-methyl benzofuran as impurity.
- the values given in the table are the average values obtained from the four samples taken during each run (after 48 h, 49 h, 50 h and 51 h).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process for preparing bisphenol A in the presence of 2-methyl benzofuran without poisoning the catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst. Moreover, the present invention provides a process for preparing polycarbonate.
Description
- This application is a U.S. national stage application, filed under 35 U.S.C. § 371, of International Application No. PCT/EP2022/053773, which was filed on Feb. 16, 2022, and which claims priority to European Patent Application No. 21158690.4, which was filed on Feb. 23, 2021. The contents of which are hereby incorporated by reference into this specification.
- The present invention relates to a process for preparing bisphenol A and a process for preparing polycarbonate.
- Bisphenol A or BPA is an important monomer in the production of polycarbonate or epoxy resins. Normally, BPA is used in the form of para,para-BPA (2,2-Bis(4-hydroxyphenol)propane; p,p-BPA). However, in the production of BPA also ortho, ortho-BPA (o,o-BPA) and/or ortho,para-BPA (o,p-BPA) may be formed. In principle, when referring to BPA, reference is made to para,para-BPA still containing low amounts of ortho, ortho-BPA and/or ortho,para-BPA.
- According to the state of the art BPA is produced by reacting phenol with acetone in the presence of an acid catalyst to give the bisphenol. In former times hydrochloric acid (HCl) was used for the commercial process of the condensation reaction. Today, a heterogeneous continuous process for the production of BPA is used in the presence of an ion exchange resin catalyst, wherein said ion exchange resin comprises a crosslinked acid functionalized polystyrene resin. The most important resins are crosslinked polystyrenes with sulfonic acid groups. Divinylbenzene is mostly used as the crosslinking agent as described in GB849965, U.S. Pat. No. 4,427,793, EP0007791 and EP0621252 or Chemistry and properties of crosslinked polymers, edited by Santokh S. Labana, Academic Press, New York 1977.
- In order to achieve a high selectivity, the reaction of phenol with acetone can be performed in the presence of suitable co-catalyst. US2005/0177006 A1 and U.S. Pat. No. 4,859,803 describe a process for preparing bisphenol A in the presence of an ion-exchange catalyst and mercaptopropionic acid or a mercaptan as co-catalyst. It is known that the catalyst deactivates over time. For example, the deactivation is described in EP0583712, EP10620041, DE14312038. One major objective for the production process is to maximize the performance and dwell times of the catalyst system. Accordingly, there is a need to identify potential poisonous substances, byproducts, impurities of educts etc. in order to deal with this objective.
- WO2012/150560 A1 teaches the use of a specific catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein the co-catalyst is chemically bound to the ion exchange resin catalyst, and also a process for catalyzing condensation reactions between phenols and ketones using such specific catalyst system. Furthermore WO2012/150560 A1 discloses a process for catalyzing condensation reactions between phenols and ketones that does not utilize a bulk promoter that is not chemically bound to the ion exchange resin catalyst.
- In the same way EP1520617 A1 describes a process for preparing bisphenols in the presence of an acidic ion-exchange resin catalyst which is modified with specific cationic compound.
- U.S. Pat. No. 8,247,619B2 describes the production of BPA based on bio-derived phenol and/or bio-derived acetone in the presence bio-derived impurities in the educts. This document solely describes the use of an ion exchange resin catalyst with attached promotor meaning that the co-catalyst is chemically (i. e. ionically) bound to the ion exchange resin catalyst. 2-Methylbenzofuran (2-MBF or MBF) was found to be a common impurity in fossil fuel-derived but also bio-derived phenol. It was found to react completely during the reaction of phenol and acetone so that no free 2-MBF was detected in the reaction product (BPA). Additionally three new MBF reaction products were observed. Furthermore, the BPA was visually pink and also the polycarbonate prepared using this BPA had a color which was not acceptable. At the same time it was found that not MBF itself was responsible for this color, but the unknown side products of MBF that are obtained during the reaction of phenol and acetone. Those unknowns could not be removed during the BPA purification. Thus, U.S. Pat. No. 8,247,619B2 concludes that the amount of MBF in the bio-derived phenol should be as low as possible in order to obtain low color BPA PC. Catalyst poisoning has not been determined in this prior art document.
- However, the removal of MBF from raw phenol (either fossil based or bio-derived) consumes time and money and thus, renders the raw phenol more expensive. In the end it increases the costs of bisphenol A and the respective polymer prepared from this bisphenol A. Moreover, the concentration of MBF in raw phenol varies depending on the supplier and their process of purification of these raw materials. This means that different raw material qualities need to be handled (e. g. another step of purification needs to be performed if the specification exceeds a certain threshold) decreasing flexibility of the process and choice of raw material supplier.
- Therefore, it was an object of the present invention to provide a process for the preparation of ortho,para-, ortho, ortho- and/or para,para-bisphenol A via condensation of phenol and acetone which is more economical than the processes of the prior art. Moreover, it was an object of the present invention to provide a process for the preparation of ortho,para-, ortho, ortho- and/or para,para-bisphenol A via condensation of phenol and acetone which is more flexible and/or which allows more flexibility in the choice of the quality of raw phenol. This flexibility should be preferably provided with respect to the concentration of 2-methyl benzofuran as impurity in raw phenol.
- At least one of the above-mentioned objects, preferably all of these objects have been solved by the present invention. Surprisingly, it has been found that a catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound (i. e. not chemically bound) to the ion exchange resin catalyst, is not susceptible to catalyst poisoning by 2-methyl benzofuran. Moreover, the prior art teaches the necessity to reduce the amount of 2-methyl benzofuran in raw phenol as low as possible. Due to the fact that the specific catalyst system of the present invention is not affected by this impurity, cheaper raw phenol can be used without the risk of reducing catalyst life time. This renders the overall process more cost effective. In addition, as less energy for purifying the raw materials is needed, the process becomes more ecologically advantageous. Moreover, the process allows more flexibility in the choice of the quality of raw phenol, especially with respect to the concentration of 2-methyl benzofuran in those raw materials.
- Furthermore, the prior art teaches that using a catalyst system which comprises an ionic bond between the ion exchange resin and the co-catalyst the MBF fully reacts during the reaction of acetone and phenol. The resulting side products of MBF have a negative impact on the color of the BPA and also the resulting BPA PC. It has been surprisingly found that when using a catalyst system, wherein the catalyst system comprises an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part, preferably at least 75 mol-% of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst, the formation of such side products of MBF can be reduced. This means that some of the MBF which is present during the reaction is also present in the resulting BPA. The prior art already confirmed that MBF as such does not have a significant impact on the color of BPA and the resulting BPA PC. Accordingly, with the catalyst system of the present invention it is possible to accept higher amounts of MBF in the raw phenol without a significant impact on the color of the resulting BPA and BPA PC. Once again this means that the overall process gets more cost effective. In addition, as less energy for purifying the raw materials is needed, the process becomes more ecologically advantageous. Moreover, the process allows more flexibility in the choice of the quality of raw phenol, especially with respect to the concentration of 2-methyl benzofuran in those raw materials.
- Accordingly, the present invention provides a process for preparing ortho,para-, ortho, ortho- and/or para,para-bisphenol A comprising the step of
-
- (a) condensing raw phenol and raw acetone in the presence of a catalyst system, wherein the catalyst system comprises an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part, preferably at least 75 mol-% of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst at the beginning of process step (a),
- characterized in that the amount of 2-methyl benzofuran present in step (a) is higher than 1 ppm with respect to the total weight of the raw phenol.
- According to the present invention reference is made to “raw phenol” and/or “raw acetone”. The term “raw” is used for the unreacted educts as applied, especially added, in the process for preparing BPA. In particular, this term is used to distinguish the phenol which is freshly added to the reaction (as raw phenol) and the phenol which is recycled in the process for preparing BPA (recycled phenol). Such recycled phenol cannot add additional MBF to the process. The same holds true for acetone which is freshly added to the reaction (as raw acetone) and acetone which is recycled in the process for preparing BPA (recycled acetone). When referring to phenol and/or acetone without any further specification it is preferred that the sum either the chemical compound as such or both raw and recycled phenol and/or raw and recycled acetone are meant.
- MBF is an impurity in raw phenol which is one of the educts of the reaction of BPA. Raw phenol can contain MBF impurities. For example, the production pathways for phenol are described in Arpe, Hans-Jürgen, Industrielle Organische Chemie, 6. Auflage, Januar 2007, Wiley-VCH. In particular the process for preparing phenol is described in Ullmann's Encyclopedia of Industrial Chemistry, chapters Phenol and Phenol derivatives. The oxidation of cumene, also known as Hock process, is by far the dominant synthetic route to phenol. Among the contaminants formed during the manufacture of phenol is 2-methyl benzofuran.
- Furthermore, in U.S. Pat. No. 8,247,619B2 at least one process is described providing bio-derived phenol which also comprises MBF as impurity.
- The process of the present invention is characterized in that the amount of 2-methyl benzofurane present in step (a) is higher than 1 ppm, preferably higher than 2 ppm, more preferably higher than 3 ppm, still more preferably higher than 4 ppm, still preferably higher than 5 ppm, still more preferably higher than 6 ppm, still more preferably higher than 7 ppm, still more preferably higher than 8 ppm, still more preferably higher than 9 ppm, still more preferably higher than 10 ppm, still more preferably higher than 11 ppm, still more preferably higher than 12 ppm, still more preferably higher than 13 ppm, still more preferably higher than 14 ppm, still more preferably higher than 15 ppm, still more preferably higher than 20 ppm, still more preferably higher than 25 ppm and most preferably higher than 50 ppm with respect to the total weight the raw phenol.
- Moreover, it is preferable that the amount of MBF present in step (a) is higher than 1 ppm and equal to or lower than 5000 ppm, more preferably equal to or lower 4500 ppm, still more preferably equal to or lower 4000 ppm, still more preferably equal to or lower 3500 ppm, still more preferably equal to or lower 3000 ppm, still more preferably equal to or lower 2500 ppm and most preferably equal to or lower 2000 ppm with respect to the total weight of the raw phenol. It is understood that the upper limits given here can be combined with the preferred lower limits given above can be combined. The skilled person knows how to determine the amount of MBF in raw phenol. For example, the amount of 2-methyl benzofuran in raw phenol can be determined according to ASTM D6142-12 (2013).
- According to the present invention “ppm” preferably refers to parts by weight.
- According to the present invention, it has been found that a side product is formed due to the presence of MBF in reaction step (a). However, not all of the MBF reacts to this impurity. This means that the MBF does not fully react to this impurity. This new side product was analyzed via MS and a molecular weight of 226 g/mol was detected. This suggests an atomic formula of C15H14O2. Without being bound to a theory, the phenol might react with the MBF. However, because no deactivation of the catalyst has been observed, this impurity (and all other possible impurities) does not seem to poison the catalyst at least at small amounts. Therefore, it is preferred that step (a) is conducted in the additional presence of at least one impurity formed due to the presence of MBF in process step (a). Moreover, those impurities can be present in process step (a) in case the phenol fraction of step (b) is recycled in process step (c).
- Still preferably, the process of the present invention is characterized in that the 2-methyl benzofuran is present throughout the whole process step (a). As has been described above, according to the present invention it has been found that when using the catalyst system of the present invention, the MBF does not fully react during process step (a). This means that some of the MBF is still present in the BPA. Preferably at least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% with respect to the MBF being present at the beginning of process step (a) are present also at the end of process step (a), preferably at the beginning of process step (b) described below. Preferably at least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% with respect to the MBF being present at the beginning of process step (a) are present in the resulting ortho,para-, ortho, ortho- or para,para-bisphenol A.
- Preferably, the process of the present invention is characterized in that the process additionally comprises the following step:
-
- (b) separating the mixture obtained after step (a) into a bisphenol A fraction comprising at least one of ortho,para-, ortho, ortho- or para,para-bisphenol A and a phenol fraction, wherein the phenol fraction comprises unreacted phenol and at least one impurity formed due to the presence of 2-methyl benzofuran in step (a).
- Preferably, the bisphenol A fraction is taken as product and/or further purified. Several variants of production processes exist to provide the bisphenol of high purity. This high purity is especially of importance for the use of BPA as monomer in the production of polycarbonates. WO-A 0172677 describes crystals of an adduct of a bisphenol and of a phenol and a method for producing these crystals and finally preparing bisphenols. It was found that by crystallizing these adducts a para,para-BPA of high purity can be obtained. EP1944284 describes the process for producing bisphenols wherein the crystallization comprises continuous suspension crystallization devices. It is mentioned that the requirements with respect to the BPA purity are increasing and that with the disclosed method a very pure BPA of higher than 99.7% can be obtained. WO-A 2005075397 describes a process for producing bisphenol A in which the water that is produced during the reaction is removed by distillation. By this method the unreacted acetone is recovered and recycled resulting in an economically favorable process.
- Preferably, the process of the present invention is characterized in that the separation in step (b) is performed using a crystallization technique. Still preferably, the separation in step (b) is performed using at least one continuous suspension crystallization device.
- It has been further described to make use of a mother liquor cycle. BPA is taken out of the solvent by crystallization and filtration after the reaction. The mother liquor typically contains 5 to 20% BPA and byproducts dissolved in unreacted phenol. Moreover, water is formed during the reaction and is removed from the mother liquor in the dewatering section. Preferably, the fraction comprising unreacted phenol is recycled for further reaction. This preferably means that the mother liquor is recycled. It is re-used as unreacted phenol in the reaction with acetone in order to give BPA. The flow of mother liquor is preferably conventionally recirculated into the reaction unit.
- Typically byproducts in the mother liquor are for example o,p-BPA, o,o-BPA, substituted indenes, hydroxyphenyl indanoles, hydroxyphenyl chromanes, substituted xanthenes and higher condensed compounds. In addition, further secondary compounds such as anisole, mesityl oxide, mesitylene and diacetone alcohol may be formed as a result of self-condensation of the acetone and reaction with impurities in the raw material.
- Due to the recycling of mother liquor byproducts accumulate in the circulation stream and can lead to an additional deactivation of the catalyst system. This means for a prolonged use of a catalyst, the impact of initial impurities in the educts have to be considered as well as the impact of possible byproducts in the reaction itself, resulting either from the reaction of phenol with acetone or from a reaction of one of the impurities.
- Still preferably, the process according to the present invention is characterized in that the process comprises the additional step of
-
- (c) using at least a part of the phenol fraction obtained in step (b) as educt in step (a).
- Still preferably, the part of the phenol fraction comprises at least 5 wt.-%, more preferably at least 10 wt.-% and most preferably at least 15 wt.-% of MBF, wherein the weight percent of MBF refers to the part of MBF as compared to the MBF being present in the raw phenol.
- In order to avoid accumulation of the introduced MBF, byproducts and/or impurities formed due to the presence of MBF in step (a) in the system several options exist. Those options include inter alia the purge stream, the waste water, the off gas and the BPA as product itself. The major one seems to be the purge stream, for example a portion of the mother liquor is discharged. Another approach comprises the passing a part of the entire amount of the circulation stream after solid/liquid separation and before or after the removal of water and residual acetone, over e. g. a rearrangement unit filled with acid ion exchanger. In this rearrangement unit some of the byproducts from BPA preparation are isomerized to give p,p-BPA. It is assumed that the new impurity which forms due to the presence of MBF in process step (a) can be at least partly removed by a purge stream. Accordingly, it is preferred that at least part of the phenol fraction obtained in step (b) is used as educt in step (a), wherein at least a part of this stream is purged. Preferably, more than 50 vol.-% of the phenol fraction obtained in step (b) is used as educt in step (a), wherein the vol.-% is based on the total volume of the phenol fraction.
- The catalyst system which can be used in the process of the present invention is known by the skilled person. Preferably, it is an acidic ion exchange resin. Such ion exchange resin can have from 2% to 20%, preferably 3 to 10% and most preferably 3.5 to 5.5% crosslinkage. The acidic ion exchange resin preferably can be selected from the group consisting of sulfonated styrene divinyl benzene resins, sulfonated styrene resins, phenol formaldehyde sulfonic acid resins and benzene formaldehyde sulfonic acid. Moreover, the ion exchange resin may contain sulfonic acid groups. The catalyst bed can be either a fixed bed or a fluidized bed.
- Furthermore, the catalyst system of the present invention comprises a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst. The sulfur containing cocatalyst can be one substance or a mixture of at least two substances. This cocatalyst is preferably dissolved in the reaction solution of process step (a). Still preferably, the cocatalyst is dissolved homogenously in the reaction solution of process step (a). Preferably, the process of the present invention is characterized in that the sulfur containing cocatalyst is selected from the group consisting of mercaptopropionic acid, hydrogen sulfide, alkyl sulfides such as ethyl sulfide and mixtures thereof. Most preferably, the sulfur containing cocatalyst is 3-mercaptopropionic acid.
- Preferably, the catalyst system of the present invention comprises a sulfur containing cocatalyst, wherein all of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst. This means that preferably all of the sulfur containing cocatalyst is added to the process step (a). According to the present invention the expression “not chemically bound” or “neither covalently nor ionically bound” refers to a catalyst system where neither a covalent nor an ionic bound between the ion exchange resin catalyst and the sulfur containing cocatalyst is present at the beginning of process step (a). However, this does not mean that at least part of the sulfur containing cocatalyst might get fixed to the heterogeneous catalyst matrix via ionic or covalent bonds. Nevertheless, at the beginning of process step (a) no such ionic or covalent bonds of the sulfur containing cocatalyst are present, but if they are formed at all, they are formed over time. Accordingly, preferably the sulfur containing cocatalyst is added to process step (a). The term “added” describes an active process step. This means, as said above, that the cocatalyst is preferably dissolved in the reaction solution of process step (a). Additionally the cocatalyst can be added at any other process step or even twice or more times at process step (a). Moreover, preferably, most of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst. This means that at least 75 mol-%, still preferably at least 80 mol-%, most preferably at least 90 mol-% of the sulfur containing cocatalyst is not chemically bound to the ion exchange resin catalyst. Here the mol-% relate to the total sum of the cocatalyst present in process step (a).
- Because MBF is a common impurity in raw phenol, it is preferred that the MBF present in step (a) is introduced into the process step (a) as impurity in the raw phenol. Nevertheless, at least part of the MBF can be present in process step (a) due to other reasons. For example, some of the MBF present in process step (a) may be present due to the recycling of phenol.
- Still preferably, the process according to the present invention is characterized in that the raw phenol which is used in process step (a) is bio-based. Still preferably, the raw phenol which comprises MBF as impurity is bio-based.
- As used according to the present invention, the term “bio-derived” or “bio-based” refers to (raw) phenol from a currently renewable resource. In particular, this term is used as opposed to phenol being derived from fossil fuels. The fact whether a raw material is bio-based, can be verified by measurements on carbon isotope levels, since the relative amounts of isotopic carbon C14 are lower in fossil-fuel materials. The skilled person knows such measurements which can be performed for example according to ASTM D6866-18 (2018) or 15016620-1 to -5 (2015).
- In another aspect the present invention provides a process for preparing polycarbonate comprising the steps of
-
- (i) obtaining a ortho,para-, ortho, ortho- and/or para,para-bisphenol A according to the process of the present invention in any embodiment or combination of preferred embodiments and
- (ii) polymerizing the ortho,para-, ortho, ortho- and/or para,para-bisphenol A obtained in step (i), optionally in the presence of at least one further monomer in order to obtain a polycarbonate.
- As explained above, the process for the production of ortho,para-, ortho, ortho- and/or para,para-bisphenol A of the present invention provides a BPA which can be obtained in a more economical and/or ecological way. Accordingly, in using this BPA as obtained with the process according to the present invention, the process for preparing polycarbonate according to the present invention is more economical and/or ecological, too.
- Reaction step (ii) is known to the skilled person. The polycarbonates can be prepared in a known manner from the BPA, carbonic acid derivatives, optionally chain terminators and optionally branching agents by interphase phosgenation or melt transesterification.
- In the interphase phosgenation bisphenols and optionally branching agents are dissolved in aqueous alkaline solution and reacted with a carbonate source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture comprising an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound. The reaction procedure can also be effected in a plurality of stages. Such processes for the preparation of polycarbonate are known in principle as interfacial processes, for example from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 page 33 et seq., and on Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, chapter VIII, page 325, and the underlying conditions are therefore familiar to the person skilled in the art.
- Alternatively, polycarbonates may also be prepared by the melt transesterification process. The melt transesterification process is described, for example, in Encyclopaedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol, 9, John Wiley and Sons, Inc. (1964), and DE-C 10 31 512. In the melt transesterification process, the aromatic dihydroxy compounds already described in the case of an interfacial process are transesterified with carbonic acid diesters with the aid of suitable catalysts and optionally further additives in the melt.
- Preferably, the process for preparing polycarbonates according to the present invention is characterized in that the process step (i) further comprises a step of purifying the ortho,para-, ortho, ortho- and/or para,para-bisphenol A in order to reduce the amount of at least one impurity formed due to the presence of MBF in step (a). As has been described above, cheaper raw phenol can be used in the process of the present invention. However, when having MBF as impurity in these cheaper raw materials, other impurities are formed. These impurities are preferably removed before the polymerization.
- Materials used in the examples:
-
catalyst acidic polymer-based resin (polystyrene-divinyl-benzene) with sulfonic acid groups, spherical beads, 4% of crosslinking, phenol Acros Organics, grade: extra pure > 99% (measured purity by GC: 99.9%) MEPA 3-mercaptopropionic acid, Sigma-Aldrich, Purity > 99% (measured purity by GC: 99.3%) acetone VWR, GPR rectapur > 99.5% (measured purity by GC: 100%, water not included) 2-methyl Sigma Aldrich, purity 99.0% benzofuran methanol Fisher Analytical grade; GC purity 99.99% - A column reactor was equipped with 150 g of the phenol-wet catalyst (volume of phenol-wet catalyst in the reactor: 210 to 230 ml). The column reactor was heated to 60° C. (catalyst bed temperature during reaction: 63° C.). A mixture of phenol, acetone (3.9 wt.-%) and MEPA (160 ppm with respect to the sum of the masses of phenol and acetone) was prepared and tempered to 60° C. This mixture was pumped into the column reactor with a flow rate of 45 g/h. The column reactor was equipped with a sampling point at the bottom. Using the aperture of the sampling point, different samples were taken during the reaction. Sampling time was 1 h and the amount of the sample taken each hour was 45 g.
- A first run (standard run) was conducted for 52 h. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken and analyzed via GC.
- A second run (impurity run) was conducted for 52 h. At the beginning of the second run 1590 ppm (with respect to the sum of the masses of phenol and acetone) of 2-methyl benzofuran was dosed to the reaction system. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken and analyzed via GC. After this a fresh mixture of acetone, phenol and MEPA was used and a third run (standard run) was conducted for 52 h. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken via a syringe and analyzed via GC. Then a fourth run (impurity run) was conducted for 52 h. At the beginning of the fourth run 1580 ppm (with respect to the sum of the masses of phenol and acetone) of 2-methyl benzofuran was dosed to the reaction system. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken and analyzed via GC. Finally, a fifth run (standard run) was conducted for 52 h. After 48 h, 49 h, 50 h and 51 h, respectively, a sample was taken and analyzed via GC.
- The gaschromatography (GC) for methanol was conducted using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 50 m×0.25 mm×0.25 μm, a temperature profile of 60° C. for 0.10 min, heating with 12° C./min to 320° C. and holding this temperature for 10.00 min; injecting 1 μl with a split of 10/1 at 300° C.); wherein the flow is 2 ml/min at an initial pressure of 18.3 psi (1.26 bar)
- The gaschromatography (GC) for 2-methyl benzofuran, phenol, para,para BPA were conducted using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 50 m×0.25 mm×0.25 μm, a temperature profile of 80° C. for 0.10 min, heating with 12° C./min to 320° C. and holding this temperature for 10.00 min; injecting 1 μl with a split of 10/1 at 300° C.); wherein the flow is 2 ml/min at an initial pressure of 18.3 psi (1.26 bar)
- The gas chromatography (GC) coupled to mass spectroscopy (MS) for identification of the unknown compound was performed using a column Agilent J&W VF-1MS (100% Dimethylpolysiloxane) of the size 30 m×0.25 mm×0.25 μm, a temperature profile of 60° C. for 0.10 min, heating with 12° C./min to 350° C. and holding this temperature for 5 min; injecting 0.5 μl with a split of 10/1 at 250° C.); wherein the flow is 1 ml/min at an initial pressure of 24.45 psi (1.685768 bar) and the mass spectrometer scans from mz35-mz 700.
- The standard run represents the reaction of acetone and phenol in the presence of the catalyst and cocatalyst to form BPA. From this the acetone conversion can be estimated including respective error bars. This conversion represented the baseline to evaluate whether the impurities influence the catalyst deactivation or not. The acetone conversion of standard runs 3 and 5 were compared to the value of standard run 1 to determine the effect of 2-methyl benzofuran on the catalyst. If the acetone conversion dropped out of this conversion, it would be proven that 2-methyl benzofuran has an effect on the BPA catalyst. In order to show that this kind of evaluation can be used to determine catalyst poisoning, a reference run was conducted using methanol as impurity. It is known from the state of the art that methanol is a known poison for the catalyst in the BPA process that is described for example in U.S. Pat. No. 8,143,456. Table 1 shows the respectively obtained results. The values given in the table are the average values obtained from the four samples taken during each run (after 48 h, 49 h, 50 h and 51 h).
-
TABLE 1 reference run with methanol first run second run third run fourth run fifth run (standard (impurity (standard (impurity (standard Substance Unit run) run) run) run) run) Acetone conversion % 82.63 78.65 81.92 78.20 79.42 Methanol IN** mg/kg — 1710 — 1660 — **The amount of methanol IN is measured before the catalyst. - As can be clearly seen from table 1, the acetone conversion of each standard run 1, 3 and 5 drops. This means that the catalyst is poisoned by methanol and the conversion cannot be recovered due to irreversible reactions which decrease the catalyst activity.
- The following table shows the results of the first run (standard run), the second run (impurity run), the third run (standard run), the fourth run (impurity run) and the fifth run (standard run) for 2-methyl benzofuran as impurity. The values given in the table are the average values obtained from the four samples taken during each run (after 48 h, 49 h, 50 h and 51 h).
-
TABLE 2 2-methyl benzofuran first run second run third run fourth run fifth run (standard (impurity (standard (impurity (standard Substance Unit run) run) run) run) run) Acetone conversion % 83.53 83.27 81.54 83.72 81.47 2-methyl benzofuran mg/kg — 1590 1580 IN** 2-methyl benzofuran mg/kg — 328.50 333.75 OUT** Unknown compounds % — 0.22 — 0.27 — **The amount of 2-methyl benzofuran IN is measured before the catalyst. The amount of 2-methyl benzofuran OUT is measured from the four samples taken during each run (after 48 h, 49 h, 50 h and 51 h; average value). - As can be seen from the results of table 2, the addition of 2-methyl benzofuran in a reaction of phenol and acetone to para,para-BPA leads to almost no drop in acetone conversion for the standard runs 1, 3 and 5. This means that MBF is no poison for the catalyst system used. This effect can be seen after each impurity run. Moreover, it can be seen that still some MBF is leaving the reactor during the impurity runs (2-methyl benzofuran OUT can be detected). This means that not all of the MBF reacts during the impurity run. Moreover, at least one unknown compound was found to a molecular weight of 226 g/mol.
Claims (15)
1. A process for preparing ortho,para-, ortho,ortho- and/or para,para-bisphenol A comprising the step of
(a) condensing raw phenol and raw acetone in the presence of a catalyst system, wherein the catalyst system comprises an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is neither covalently nor ionically bound to the ion exchange resin catalyst at the beginning of process step (a),
wherein the amount of 2-methyl benzofuran present in step (a) is higher than 1 ppm with respect to the total weight of the raw phenol.
2. The process according to claim 1 , wherein the amount of 2-methyl benzofuran present in step (a) is higher than 1 ppm and equal to or lower than 5000 ppm with respect to the total weight of the raw phenol.
3. The process according to claim 1 , wherein step (a) is conducted in the additional presence of at least one impurity formed due to the presence of 2-methyl benzofuran in step (a).
4. The process according to claim 1 , wherein the 2-methyl benzofuran is present throughout the whole process step (a).
5. The process according to claim 1 , wherein the process further comprises the following step:
(b) separating the mixture obtained after step (a) into a bisphenol A fraction comprising at least one of ortho,para-, ortho,ortho- or para,para-bisphenol A and a phenol fraction, wherein the phenol fraction comprises unreacted phenol and at least one impurity formed due to the presence of 2-methyl benzofuran in step (a).
6. The process according to claim 5 , wherein the separation in step (b) is performed using a crystallization technique.
7. The process according to claim 5 , wherein the process further comprises the additional step of
(c) using at least a part of the phenol fraction obtained in step (b) as educt in step (a).
8. The process according to claim 1 , wherein the sulfur containing cocatalyst is selected from the group consisting of mercaptopropionic acid, hydrogen sulfide, alkyl sulfides and mixtures thereof.
9. The process according to claim 1 , wherein the 2-methyl benzofuran present in step (a) is introduced into the process step (a) as impurity in the raw phenol.
10. The process according to claim 9 , wherein the raw phenol is bio-based.
11. A process for preparing polycarbonate comprising the steps of
(i) obtaining a ortho,para-, ortho,ortho- and/or para,para-bisphenol A according to the process of claim 1 and
(ii) polymerizing the ortho,para-, ortho,ortho- and/or para,para-bisphenol A obtained in step (i).
12. The process according to claim 12 , wherein the process of step (i) further comprises a step of purifying the ortho,para-, ortho,ortho- and/or para,para-bisphenol A in order to reduce the amount of at least one impurity formed due to the presence of 2-methyl benzofuran in step (a).
13. The process of claim 1 , wherein at least 75 mol % of the sulphur containing cocatalyst of the catalyst system is neither covalently nor ionically bound to the ion exchange resin catalyst at the beginning of process step (a).
14. The process of claim 8 , wherein the alkyl sulfide is ethyl sulfide.
15. The process of claim 11 , wherein step (ii) is performed in the presence of at least one further monomer in order to obtain a polycarbonate.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21158690 | 2021-02-23 | ||
EP21158690.4 | 2021-02-23 | ||
PCT/EP2022/053773 WO2022179900A1 (en) | 2021-02-23 | 2022-02-16 | Process for preparing bisphenol a (bpa) in the presence of 2-methyl benzofuran |
Publications (1)
Publication Number | Publication Date |
---|---|
US20240076257A1 true US20240076257A1 (en) | 2024-03-07 |
Family
ID=74732598
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/270,646 Pending US20240076257A1 (en) | 2021-02-23 | 2022-02-16 | Process for preparing bisphenol a (bpa) in the presence of 2-methyl benzofuran |
Country Status (7)
Country | Link |
---|---|
US (1) | US20240076257A1 (en) |
EP (1) | EP4298081A1 (en) |
JP (1) | JP2024507889A (en) |
KR (1) | KR20230149816A (en) |
CN (1) | CN116867761A (en) |
TW (1) | TW202302502A (en) |
WO (1) | WO2022179900A1 (en) |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1031512B (en) | 1955-12-21 | 1958-06-04 | Bayer Ag | Process for the production of high molecular weight fiber and film forming polycarbonates |
JPS5518495A (en) | 1978-07-24 | 1980-02-08 | Rohm & Haas | Method of manufacturing polymer composition and polymer bead |
US4427793A (en) | 1980-01-28 | 1984-01-24 | Rohm And Haas Company | Vinylbenzyl alcohol polymer beads and thermally crosslinked derivatives thereof |
US4859803A (en) | 1988-05-16 | 1989-08-22 | Shell Oil Company | Preparation of bisphenols |
DE4227520A1 (en) | 1992-08-20 | 1994-02-24 | Bayer Ag | Process for the preparation of bisphenols |
DE4312039A1 (en) | 1993-04-13 | 1994-10-20 | Bayer Ag | Optimized ion exchange beds for bis-phenol-A synthesis |
DE4312038A1 (en) | 1993-04-13 | 1994-10-20 | Bayer Ag | Multiple regenerable ion exchange resins with low alkyl SH group occupancy |
DE10015014A1 (en) | 2000-03-27 | 2001-10-04 | Bayer Ag | Process for the preparation of bisphenols |
JP4147202B2 (en) | 2003-09-30 | 2008-09-10 | 三井化学株式会社 | Modified acidic ion exchange resin catalyst and method for producing bisphenols using the same |
DE102004005726A1 (en) | 2004-02-05 | 2005-08-25 | Bayer Materialscience Ag | Drainage of circulatory streams in the production of bisphenol A |
DE102004005722A1 (en) | 2004-02-05 | 2005-08-25 | Bayer Materialscience Ag | Process for the preparation of bisphenols with optimal filling of the reactor with catalyst |
DE102007001427A1 (en) | 2007-01-09 | 2008-07-10 | Bayer Materialscience Ag | Making high-purity Bisphenol A from phenol and acetone, e.g. for polycarbonate production, involves separating the Bisphenol A-phenol adduct by continuous suspension crystallisation |
CN101790505B (en) | 2007-08-29 | 2013-12-11 | 陶氏环球技术公司 | Method of reducing methanol in recycle streams in bisphenol-a-production process |
US8247619B2 (en) | 2008-12-11 | 2012-08-21 | Sabic Innovative Plastics Ip B.V. | BPA and polycarbonate made from renewable materials |
WO2012150560A1 (en) | 2011-05-02 | 2012-11-08 | Sabic Innovative Plastics Ip B.V. | High purity bisphenol a and polycarbonate materials prepared therefrom |
-
2022
- 2022-02-16 US US18/270,646 patent/US20240076257A1/en active Pending
- 2022-02-16 JP JP2023550689A patent/JP2024507889A/en active Pending
- 2022-02-16 WO PCT/EP2022/053773 patent/WO2022179900A1/en active Application Filing
- 2022-02-16 KR KR1020237028092A patent/KR20230149816A/en unknown
- 2022-02-16 CN CN202280016458.9A patent/CN116867761A/en active Pending
- 2022-02-16 EP EP22704393.2A patent/EP4298081A1/en active Pending
- 2022-02-21 TW TW111106151A patent/TW202302502A/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2022179900A1 (en) | 2022-09-01 |
CN116867761A (en) | 2023-10-10 |
TW202302502A (en) | 2023-01-16 |
JP2024507889A (en) | 2024-02-21 |
KR20230149816A (en) | 2023-10-27 |
EP4298081A1 (en) | 2024-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20050176918A1 (en) | Production of bisphenol a with reduced isomer formation | |
JP2006509818A5 (en) | ||
US20240076257A1 (en) | Process for preparing bisphenol a (bpa) in the presence of 2-methyl benzofuran | |
US20240116839A1 (en) | Process for preparing bisphenol a (bpa) in the presence of acetophenone | |
US20240076256A1 (en) | Process for preparing bisphenol a (bpa) in the presence of alpha-methylstyrene | |
US20240059639A1 (en) | Process for preparing bisphenol a (bpa) in the presence of at least two impurities | |
US20220259124A1 (en) | Process for preparing bisphenole a (bpa) in the presence of hydroxyacetone | |
US20240109831A1 (en) | Process for preparing bisphenol a (bpa) in the presence of benzene | |
WO2022179904A1 (en) | Process for preparing bisphenol a (bpa) in the presence of cumene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: COVESTRO DEUTSCHLAND AG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:UY, JERICO JAYSON;SLUYTS, ERIK;SIGNING DATES FROM 20230419 TO 20230506;REEL/FRAME:064279/0140 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |